JPH02121985A - Fluorescent whitening agent - Google Patents

Abstract

NEW MATERIAL: A compd. represented by formula I [wherein R¹ and R³ are each 1-8C alkyl or a group represented by formula II [wherein m is 0-10; q is 1 or 2 provided when m is 0, then q is 1; and X is COOR⁹, OR¹⁴ (wherein R⁹ is H, an alkali metal ion, etc.; and R¹⁴ is H, 1-18C alkyl, etc.), etc.]; R² and R4 are each a group represented by formula II, or when R¹ and R³ are each a group represented by formula II, then R² and R⁴ are each a group represented by formula II, cyclopentyl, etc.; and R⁵ and R⁶ are each II, methyl, etc.}.

EXAMPLE: 2,5-bis-[7-t-butyl-5-(2-methoxycarbonyl-1-ethyl)benzoxazol-2-yl]thiophene.

USE: A fluorescent brightener, useful esp. for photographic recording materials.

PROCESS: For instance, 1 mol.-equivalent of a thiophenedicarboxylic acid represented by formula III is reacted with 2 mol.-equivalents of an o- aminophenol represented by formula IV and/or V in the presence of an acidic catalyst (e.g. boric acid) in an inert gas atmosphere in a solvent (e.g. DMF) at 160-260°C.

COPYRIGHT: (C)1990,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel 2°5-bis-benzoxazolyl-thiophenes which can be used as fluorescent brighteners for organic materials, especially imaging and recording materials.

2.5-Bis-benzoxazolyl-thiophenes have long been known as fluorescent brighteners for organic materials, and several members of this class are commercially available. 2.5-
Bis-benzoxazolyl thiophene, its preparation and its use as a fluorescent brightener are described, for example, in U.S. Pat.
36.773, 3,449.257 and 4,267
．． It is described in No. 343. It is also known to add fluorescent brighteners containing compounds from the above-mentioned classes to photographic recording materials, such as photographic paper, in order to improve the white impression and brightness;
No. 762, No. 3,416,923, No. 3.418.1
No. 27 and No. 3,449,257, British Patent No. LO7
See No. 2,915 and Japanese Patent No. 61-124.939. The incorporation of brighteners into appropriate layers of the recording material presents special problems. Therefore, there is a need for a material that can be easily incorporated into photographic recording materials as a fluorescent brightener and that develops good brightness in the material. Moreover, there is still a very general need for new fluorescent brighteners for a wide variety of applications.

Therefore, the first subject of the present invention is the following formula: [wherein R+ and R3 are each independently an alkyl group having 1 to 8 carbon atoms, a cyclopentyl group, a cyclohexyl group, an aralkyl group having 7 to 9 carbon atoms] , phenyl group or the following formula: C, R2,, I-q (X), (, n) (wherein m represents a number from 0 to 10, q represents 1 or 2, m represents 0 (in which case q represents 1), Rz and R4 each independently represent a group represented by the above formula II, or R1 and R3 each represent a group represented by the above formula II , R2 and R4 each independently represent an alkyl group having 1 to 8 carbon atoms, a cyclopentyl group,
It can also represent cyclohexyl, C7 -C9 aralkyl or phenyl, R5 and Rh
each independently represents a hydrogen atom, a methyl group, an ethyl group, or
or - taken together represent a trimethylene group or a tetramethylene group, and X is a) of the following formula:
an alkali metal ion or equivalent alkaline earth metal ion, a C1-C30 alkyl group, a C1-C18 hydroxyalkyl group, a C3-C20 alkyl group, or at least one C1-C30 alkyl group; −
a hydroxyalkyl group of 3 to 20 carbon atoms, unsubstituted or substituted with OH and/or an alkyl group of 1 to 4 carbon atoms;
2 cycloalkyl group, C2 to C30 alkenyl group, C7 to C15 aralkyl group,
Glycidyl group, furfuryl group or the following formula: -CH2-
CH(OH)-R10 (wherein R1+1 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aralkyl group having 7 to 9 carbon atoms, or the following formula: CH,OR" (
In the formula, R1+ is an alkyl group having 1 to 18 carbon atoms,
cyclohexyl group, phenyl group, tolyl group or benzyl group), or R9 represents a group represented by the following formula:
f and R11+ represent the meanings shown in d) below)
b) a group represented by the following formula: -C
ONR"R13 (wherein R12 and R13 are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkyl group having 3 to 20 carbon atoms with at least one 10- interposed therebetween,
Unsubstituted or C1 -C4 alkyl and/or OH-substituted C5 -C12 cycloalkyl, phenyl or C1 -C12 alkyl, C1 -C4 represents an alkoxy group and/or a phenyl group substituted with a halogen atom; an alkenyl group having 3 to 18 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or a hydroxyalkyl group having 2 to 4 carbon atoms; or RIz
and RIff together represent an alkylene group having 4 to 5 carbon atoms or 10- or the following formula: -N CR"
) - (wherein RI 5 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cyclohexyl group, or a cyclohexyl group having 2 carbon atoms)
alkenyl group having 7 to 6 carbon atoms, phenyl group or alkylphenyl group having 7 to 12 carbon atoms or 7 carbon atoms
C) a group represented by the following formula: OR+4 or -QJ
Rh.

(wherein R'' is a hydrogen atom, a C1-C18 alkyl group, a C5-C12 cycloalkyl group, a carbon atom substituted with OH and/or a C1-C4 alkyl group) represents a cycloalkyl group having 5 to 12 carbon atoms, an alkenyl group having 3 to 18 carbon atoms, a phenyl group or an aralkyl group having 7 to 20 carbon atoms, and R2O is an alkyl group having 1 to 18 carbon atoms, a cyclohexyl group , a C2-C18 alkenyl group, a phenyl group, a C7-C12 alkylphenyl group or a C7-12 aralkyl group, d) the following formula: - P (0) (OR”) (OR”) or -P (0) (OR16) -R18 (wherein, R16 is a hydrogen atom or 1 to 1 carbon atom
2 represents an alkyl group, RI'7 represents an alkyl group having 1 to 12 carbon atoms, and R1!1 represents an alkyl group having 1 to 12 carbon atoms or a phenyl group), or ( In the formula, R19 represents an alkyl group having 1 to 12 carbon atoms.

Among the groups of formula (1), it should be noted that, for example, the following formula: (wherein n represents 2 to 8, k represents 1 or 2, and R'r and R8 each independently represent carbon represents an alkyl group having 1 to 5 atoms, or R1 is a group: C, H, .
-1 forms a cycloalkyl ring having 5 to 6 carbon atoms. R1 and R3
When is a group of the above formula (1), it is preferably a group of (2).

The alkyl substituents of formula I are straight-chain or branched-chain alkyl groups. The same applies to substituted or heteroatom-mediated alkyl groups. Similarly, alkylene groups as well as substituted or substituted alkylene groups with an intervening petero atom can be straight-chain or branched.

Substituent R as C 1 -C 30 alkyl group
Examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 2-butyl group, 3-butyl group,
n-pentyl group, tertiary amyl group, n-hexyl group, n-
heptyl group, n-octyl group, 2-ethylhexyl group,
1.1.3.3-tetramethylbutyl group, n-nonyl group, n-decyl group, 2,7-dimethyloctyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n
-hexadecyl group, n-octadecyl group, eicosyl group, tocosyl group or triacontyl group. Examples of alkyl substituents R with shorter chains are those mentioned above with up to the corresponding number of carbon atoms. R1 and/or R3 are preferably C1 -C4 alkyl, in particular tert-butyl. R7 and R11 are preferably C1 -C2 alkyl, especially methyl. Alkyl 5R' preferably has 1 to 18 carbon atoms.

R1 is an aralkyl group having 7 to 9 carbon atoms;
R2, R3, R4 and R1 (an example of 1 is a benzyl group,
They are a phenethyl group, an α-methylbenzyl group, and an α,α-dimethylbenzyl group.

In 2), n is, for example, 2 to 4, especially 3;
k is preferably 1. In formula (2), m is in particular O to 6 and q is in particular 1. When k or q is 1, X is preferably a terminal group. When q or k is 2, X may be bonded to the same or different carbon atoms. Alkyl group R having 3 to 20 carbon atoms
", R" and R11 are one or more 10-
for example, 2 methoxyethyl group,
2-ethoxyethyl group, 2-n-propoxyethyl group,
2-n-butoxyethyl group or represented by the following formula: (wherein Ro represents H or CH, R represents an alkyl group having 1 to 4 carbon atoms, and X represents 1 to 6) groups, especially 2-(2-methoxyethyl)ethyl, 2-(2ethoxyethyl)ethyl and 2-(2
-butoxyethyl)ethyl group. Examples of the hydroxyalkyl group R9 in which -〇- is present include the above-mentioned hydroxyalkyl group R9 substituted with one or more, preferably 1 to 3, particularly one hydroxyl group, and in which ``'alkyl group'' and -〇- are present in the hydroxyl group R9. The groups mentioned as "alkyl groups" are possible.

Unsubstituted or OH and/or C1 to C4
Cycloalkyl groups having 5 to 12 carbon atoms substituted with an alkyl group R9, R''R13 and R are, for example, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, an adamantyl group, a cyclododecyl group, - or 4-hydroxycyclohexyl group, or 2-23- or 4-methylcyclohexyl group. Unsubstituted cycloalkyl group is preferred;
Particular preference is given to the cyclopentyl group, especially the cyclohexyl group and the 2- or 4-methylcyclohexyl group.

C2 -C30 alkenyl R9 is, for example, vinyl, allyl, n-but-2-enyl, 2-methyl-prop-2-enyl, n-pent-2-enyl, n- hex-2-enyl group, n-hex-2,4-
Genyl group, n-ace-9-enyl group, n-undecenyl-10-yl group, n-ocdadece-9-enyl group or n-octaace-1-fuenyl group. Other R radicals are alkenyl radicals, for example radicals that are identical in each case depending on the possible carbon chain length. R9 as alkenyl is preferably C1 -C18 alkenyl.

R9, R12 as C7-C15 aral or C7-12 aralkyl,
R'', R14 and R'' are, for example, naphthyl-C1-C5 alkyl group or phenyl-C1-C9 alkyl group or naphthyl-C1-C9 alkyl group.
-C2 alkyl group or phenyl-C1 -C6 alkyl group, preferably phenyl-C1 -C3 alkyl group. Examples of these are those mentioned above as aralkyl groups having 7 to 9 carbon atoms.

Halogen is CI, F or Br, especially CI.

C4-C5 alkylene W RIZ and R1
3 forms a pyrrolidine ring or piperidine ring together with the N atom, and an alkylene group having 4 to 6 carbon atoms with -〇- or -NCR"')- is combined with the N atom, For example, a 5- to 7-membered heterocycle with 2 or 1 nitrogen atom and 1 oxygen atom is formed as ring members, such as a piperazine ring or a morpholine ring. In each case, the piperazine ring can have a substitution i RI %.

In 2I, R1 and R3 and Rz and R4 are each preferably the same.

Preferred compounds of formula I include R1 and/or R3 in which R1 and/or R3 are a C1-C4 alkyl group, a cyclohexyl group or a group represented by the above formula (1) (especially the above formula (2)), especially a C1-4 alkyl group. group (particularly preferably a tert-butyl group), a cyclohexyl group, or a group represented by the following formula: Here, R'
and R3 are particularly preferably C1 -C4 alkyl, especially tert-butyl.

In the above formula (1), R1 and R3 represent an alkyl group having 1 to 4 carbon atoms, a cyclohexyl group, a benzyl group, or a group represented by the above formula II, and Rz and R4 represent a group represented by the above formula II, or When R represents a group represented by the above formula II, it can also represent an alkyl group having 1 to 8 carbon atoms, a cyclopentyl group, a cyclohexyl group, or a phenyl-alkyl group having 1 to 3 carbon atoms, and m is O. R5 and R6 each independently represent a hydrogen atom, a methyl group or an ethyl group, and R9 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cyclopentyl group, a cyclohexyl group, or a cyclohexyl group having 2 to 18 carbon atoms. alkenyl group, phenyl - C1 -C3 alkyl group, furfuryl group, C3 -C18 alkyl group with 1 to 4 intervening 10- groups, or 0) (O alkyl having 1 to 6 carbon atoms) represents a group represented by 2 (in the formula, p represents 1 to 6), and R12 and RI3 are each independently a hydrogen atom and 1 to 18 carbon atoms; alkyl group, cyclopentyl group,
Cyclohexyl group, phenyl group, carbon number 1 to 4
represents an alkyl group, a methoxy group and/or a phenyl group substituted with a chlorine atom, an alkenyl group having 3 to 18 carbon atoms, a benzyl group or a hydroxyalkyl group having 2 to 4 carbon atoms, or R12 and R13 are Together, they represent an alkylene group having 4 to 5 carbon atoms or an alkylene group having 4 to 5 carbon atoms interposed with 10-1-NH- or -N(CH)-, and RII is a hydrogen atom, carbon represents an alkyl group having 1 to 8 atoms, a cyclohexyl group, an alkenyl group having 3 to 6 carbon atoms, a phenyl group, or a benzyl group, and RI5 is an alkyl group having 1 to 8 carbon atoms, a cyclohexyl group, a cyclohexyl group, or an alkenyl group having 3 to 6 carbon atoms; 6 alkenyl group, phenyl group, tolyl group or benzyl group, RIth represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R1'? Special mention should also be made of the compounds in which is C1 -C8 alkyl, RII is C1 -C8 alkyl and RII is C1 -C8 alkyl. In the above formula I, the substituent X is particularly of the following formula C0
It is preferable to represent a group represented by NR"R" or -COOR'.

In the above formula I, R1 and/or R4 represent a group in the above formula (1), q represents 1 or 2, and m represents 0 to 6, or R1 and/or R3 are represented by the above formula II; Special mention should also be made of compounds in which R2 and/or R4 are C1 -C8 alkyl, cyclopentyl, cyclohexyl or phenyl-C1 -C3 alkyl.

In this case too, it is preferred that R2 and R4 are the same.

R5 and R6 preferably each independently represent a hydrogen atom, a methyl group or an ethyl group.

In the above formula I, R' and R3 are the same, and the number of carbon atoms is 1
to 4 alkyl group or a group represented by the above formula II (
Preferably, in the above 2), R7 and R8 have 1 carbon atom.
represents an alkyl group of 2 to 4, n represents 2 to 4,
and R2 and R4 are the same and represent a group represented by the above formula II, or when R1 and R3 represent a group represented by the above formula II, R2 and R4 can also represent an alkyl group having 1 to 4 carbon atoms, m represents 0 to 6, and 1 to 18 alkyl group, C3 to C18 alkenyl group, furfuryl group, cyclohexyl group, phenyl-C1 to C3 alkyl group, 3 to 4 carbon atoms interposed to 18 alkyl groups, or the following formula (CH,)
,, P (0) (O alkyl having 1 to 4 carbon atoms) represents a group represented by 3 (in the formula, p' represents 1 to 4), and R1! It is particularly important that RII and RII each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. Among these compounds, in the above formula l, R1
and R3 represents an alkyl group having 1 to 4 carbon atoms or a group represented by the above formula II, and R2 and R4 represent the above formula I
When R1 and R3 represent a group represented by I, or R1 and R3 represent a group represented by the above formula II, R2 and R4 can also represent an alkyl group having 1 to 4 carbon atoms, and m is O to 6, and X represents the following formula: C0OR" (wherein R9 has 1 to 1 carbon atoms)
an alkyl group having 8 carbon atoms, an alkenyl group having 3 to 18 carbon atoms or 3 carbon atoms with 1 to 3 10- groups present;
More preferred are compounds representing from 1 to 12 alkyl groups.

As already mentioned, compounds of formula I in which R1 and R3 each represent a tert-butyl group are particularly preferred.

In the dissolved or finely dispersed state, the thiophene compounds of formula I exhibit significant fluorescence. They can therefore be used for the fluorescent whitening of many materials, especially organic materials. The invention therefore provides the use of compounds of formula I for the fluorescent whitening of organic materials, as well as organic materials containing at least one compound of formula I and at least one compound of formula
It also relates to a process for the fluorescent whitening of organic materials, characterized in that compounds of the invention are mixed into or applied to these materials.

Organic materials that can be fluorescently brightened with the compounds of formula I according to the invention include synthetic, semi-synthetic or natural, especially polymeric materials.

The following groups of organic materials are exemplified to the extent that their fluorescent whitening action may be possible, and are not intended to limit the invention.

I Synthetic organic polymeric materials: a) Polymerization products, i.e. homopolymers or copolymers, and post-treatment compounds thereof, e.g. crosslinked products, based on organic compounds having at least one polymerizable carbon-carbon double bond. , grafting or degradation products, polymer formulations, or products obtained by modification of the reactive groups, such as α,β-unsubstituted carboxylic acids or derivatives of those carboxylic acids, especially acrylic compounds (e.g. acrylic esters, acrylic acid , acrylonitrile,
polymers based on olefinic hydrocarbons (e.g. evaporated ethylene, propylene, styrene or dienes, and so-called ABS resins), as well as vinyl compounds and vinylidene compounds (acrylamides and their derivatives or methacrylic homolayers); For example, vinyl chloride, vinyl alcohol, vinylidene chloride).

b) Polymerization products obtained by ring opening, such as polyamides of the polycaprolactam type, and also polymers obtained by polymerization addition or polycondensation, such as polyethers or polyacetals.

C) Polycondensation products or precondensates based on difunctional or polyfunctional compounds having condensable groups, homocondensation products and cocondensation products thereof, and post-treatment products, e.g. polyesters. , especially saturated polyester (
(e.g. ethylene glycol terephthalate polyesters) or unsaturated polyesters (e.g. maleic acid/dialcohol polycondensation products and their crosslinked products with vinyl monomers polymerizable to them), undifferentiated and differentiated polyesters. (plus those based on polyhydric alcohols, e.g. alkyd resins),
d) polymers such as polyamides (e.g. hexamethylene diamine adipate), maleate resins, melamine resins, premixes and their homologs, polycondensates and silicones; and d) polyurethanes (crosslinked and uncrosslinked) and epoxy resins. appendix.

■ Semi-synthetic organic materials, such as cellulose esters esterified to various degrees (so-called 21/2-acetate,
triacetate) or cellulose ethers, regenerated cellulose (viscose, cupramonium cellulose),
or their post-processing products, and casein plastics.

■Natural organic materials of animal or vegetable origin, such as those based on cellulose or proteins, such as cotton, wool, linen, silk, natural resin, starch and casein.

The organic material to be fluorescently brightened can be in very different processing states (raw material, semi-finished product or finished product). On the other hand, they can be of very diverse structures. That is to say, for example, mainly three-dimensional objects, plates, sections, injection moldings, various workpieces, chips, granules or foams, as well as mainly two-dimensional structures, such as films, sheets, finishing materials, Covers, impregnations and coatings, or predominantly one-dimensional conditions such as filaments, fibers, flocks and wires. On the other hand, the materials can also be in the amorphous state of a wide variety of homogeneous or non-uniform dispersions, such as powders, solutions, emulsions, dispersions, latices, pastes or waxes.

Textile materials include, for example, endless filaments (stretchable or non-stretchable), staple fibers, flocks, skein materials, textile filaments, yarns, twisted yarns,
Non-woven fabrics, felts, battings, flocked structures or knitted fabrics, or textile composites, knitted structures and also paper, cardboard or paper valves.

The compounds used according to the invention are of particular interest for the treatment of textile organic materials, in particular textile fabrics.

When fibers, which can be in the form of staple fibers or endless filaments, knitted fabrics, knitted fabrics, knitted fabrics, non-woven fabrics, flock materials or composites, are fluorescently whitened according to the invention, the respective compounds are finely dispersed. It is advantageous to carry out the process in an aqueous medium in the form of a suspension (suspension, so-called microdispersion, if appropriate a solution). If desired, dispersants, stabilizers, wetting agents and other auxiliaries can also be added during processing.

Depending on the type of fluorescent whitening compound used, it is known to be advantageous to carry out the process in neutral or alkaline or acidic baths. Processing is typically carried out at a temperature of about 20-140°C, for example at or near the boiling point of the bath (about 90°C). According to the invention, solutions or emulsions in organic solvents can also be used for finishing textile textures. this is,
So-called solvent staining (Foulard thermofi)
xingapplication++ exhaus
tion dyeing methods indye
It is carried out using the staining technique of ing machines).

The novel fluorescent brighteners according to the invention can also be used, for example, for the whitening of paper bulbs, in particular for example in the presence of cationic fixers and other additives.

The novel fluorescent brighteners according to the invention can also be added to or incorporated into the material during or after molding. Thus, they can be added to pressure-molding or injection-molding compositions, for example during the production of films, sheets (for example by rolling hot into polyvinyl chloride) or during molding.

If the shaping of fully synthetic or semi-synthetic organic materials is carried out via spinning processes or spinning compounds, the fluorescent brighteners are applied by the following method.

Addition to starting materials (e.g. monomers) or intermediates (e.g. precondensates, prepolymers), i.e. before or during polymerization, polycondensation or polyaddition, to polymer chips or polymer granules for a spinning composition. - Bath dyeing of polymer chips or polymer grains for spinning compositions - Controlled addition to the spinning melt or spinning solution - Addition of the novel fireflies according to the invention to the tow before stretching Photobrighteners can also be used, for example, in the following application forms.

a) in admixture with dyes (shading) or pigments (colored pigments or in particular, e.g. white pigments) or in dye baths;
Added to printing paste, discharge paste or resist paste, and further as dye, post-treatment of print or discharge print.

b) Mixed with so-called carriers, wetting agents, plasticizers, swelling agents, antioxidants, light stabilizers, heat stabilizers and chemical bleaches (chlorine bleaches, bleach bath additives).

C) Mixed with cross-linking agents, finishing agents (e.g. starch or synthetic finishes) and a wide variety of textile finishing methods, especially anti-wrinkle finishes such as synthetic resin finishes (e.g. wash-and-wear, permanent press, no-iron) finishing), and further combined with flame retardant, soft handles, stain-spinning or anti-wear finishes.

d) into dissolved or dispersed polymer carrier materials (polymerization products, polycondensation products or polyaddition products) for use, e.g. as paints, impregnating agents or binders (solutions, dispersions,
Incorporation of fluorescent brighteners into textiles, non-wovens, paper and leather (emulsions) for textiles, non-wovens, paper and leather.

e) As an additive to a wide variety of industrial products to improve their marketability (e.g. to improve the appearance of soaps, detergents and pigments).

f) In combination with other substances exhibiting a fluorescent whitening effect.

g) in spinning bath formulations, i.e. as additives to spinning baths as used to improve slippage for further processing of synthetic fibers or in special baths before stretching of the fibers, e.g. in the so-called gel state; As a post-treatment agent for wet-spun polyacrylic fibers.

h) As scintillators for various purposes of photographic nature, such as electrophotographic reproduction or high sensitivity.

i) in skin dyes depending on the substituent j) in pressure intensifying screens for medical radiography; however, they are especially suitable for example Re5
EARCH DISCLOSURE 28704 (M
Arch 1988), it is suitable for use in radiation image storage screens that can be excited by light.

k) As a dyeing additive in refrigerants and as a leak detection agent in cooling systems.

When a brightening process is combined with a textile treatment or finishing process, the combined process often involves a suitable stabilizing formulation containing a fluorescent brightener in a concentration that provides the desired brightening effect. It is advantageously carried out using

In some cases, the brightener becomes fully active by post-treatment. This treatment can be, for example, chemical (eg acid treatment), thermal or a combination of chemical/thermal treatments.

Thus, for example, in the fluorescent whitening of some textile materials, such as polyester fibers, the method of using the fluorescent brighteners according to the invention involves applying an aqueous dispersion (if appropriate solution) of the brightener to the fibers. , advantageously carried out at a temperature below 75 °C, e.g. room temperature, followed by a heat treatment of 100" C to dry them. In this case, the impregnation is usually carried out at a moderately elevated temperature, e.g. at least It is also recommended to dry the fibrous material at 60"C to 130C for short periods of time. After that, heat treatment in dry state for 120 to 225
°C, for example by dry heating, ironing in the indicated temperature range, or dry high heat treatment above. The drying and drying heat treatment can be carried out immediately thereafter or can be carried out in combination in a one-step working process.

The amount of the novel fluorescent whitening agent used according to the invention varies within a wide range for the material subjected to the fluorescent whitening action. A clear and lasting effect is achieved even in very small quantities. In some cases, even small amounts such as o,ooot weight percent may be achieved. However, amounts of up to about 0.8 significant percent, and optionally up to 2 weight percent, are suitable. For most practical purposes, 0.001 to 0.5 significant%, especially 0.0
1 to 0.5% by weight, for example 0.05 to 0.2% by weight, is preferred.

For various reasons, fluorescent brighteners are often not used alone, i.e. in pure form, but with a wide variety of auxiliaries and extenders, such as anhydrous sodium sulfate, sodium sulfate decahydrate, sodium chloride, carbonate. It is advantageous to use sodium, alkali metal pyrophosphates, such as sodium or potassium tripolyphosphate, or as a mixture with alkali metal silicates.

Furthermore, the compounds of II according to the invention can be used in coating materials, in particular in finishes. Various dyes are an important field of application in the technical field. The invention therefore furthermore relates to such materials containing at least one compound (2). Particularly advantageously, the coating materials and finishes are based on photopigments, especially white pigments, in which case the whitening effect is very pronounced.

The use of the compounds of the formula I according to the invention is particularly preferred in all types of finishing agents, where they are applied, for example, to metal parts, plastic parts or wood parts.

Examples of these are shown below.

These resins are thermally crosslinkable polyester resins, alkyd resins, acrylic resins, acrylic/alkyd resins, or melamine resins, which are sintered at a temperature of 80° C. or higher, optionally with the addition of an acidic catalyst.

Two-component polyurethane finishes based on acrylic resins containing monohydroxyl groups and acrylic resins containing aliphatic or aromatic isocyanate groups or based on hydroxyl groups and/or polyether resins and aliphatic or aromatic isocyanates agents, one-component finishes based on blocked isocyanates which are not blocked during one sintering step, two-component finishes based on (poly)ketimines and aliphatic or aromatic isocyanates, - carboxy or amine groups. a two-component finishing agent based on polyacrylates and epoxides containing - (poly)ketimine and unsaturated polyacrylate or Two-component finishes based on polyacetoacetate resins, - two-component finishes based on (poly)ketimine and methyl methacrylamide glycolate, - oxazolidines and unsaturated polyacrylates or aliphatic or aromatic isocyanates. Two-component finishes based on monounsaturated polyacrylates and malonates, - based on thermoplastic polyacrylate resins or non-self-crosslinking polyacrylate resins in conjunction with etherified melamine paddle resin A two-component finishing agent. Non-self-crosslinking polyacrylate resins are available, for example from H. Kittel Lehrbu
Ch der Lacke und Beschich
(Textbook of Finis)
volume I
+ 2 parts, 712 true.

- Finishing systems based on siloxane modified acrylates, comprising resins from the group consisting of non-modified or modified alkyd resins, thermoplastic acrylic resins, acrylic/alkyd resins, polyester resins and crosslinked epoxide resins, and epoxy crosslinked acrylic resins and polyester resins. Room-temperature-curing systems based on polyvinylidene fluoride-based paints, in fact the finishes are either in the form of an organic layer or an aqueous layer. However, it is likewise possible to use the compounds according to the invention as powder finishing agents in a manner known per se.

Furthermore, the use of the compounds according to the invention in finishing agents is preferred, and the initiation of the crosslinking step is carried out by high-energy irradiation.

Examples thereof consist of one or more unsaturated compounds. These compounds can contain one or more unsaturated olefinic double bonds and are in the form of small molecules (monomers).
Or it may be a polymer type (oligomer).

Finishing systems are known to those skilled in the art and can be one-component, two-component or three-component systems.

Curing is performed by methods known to those skilled in the art.
This takes place, for example, by adding photoinitiators and activating them within defined areas or by electron beam curing.

Here, all finishes are applied as one-coat or two-coat finishes. A two-coat finish is to be understood as meaning one obtained by application as a clear coat to a metallic effect base coat or an unpigmented base coat.

Thereafter, the compound according to the invention is applied to a colored base coat (
(metallic or shaded) and/or within the clear coat, preferably within the clear coat.

The compounds according to the invention are preferably introduced into wet-effect finishes, powder finishes or radiation-curable finishes before sintering or hardening.

The finish can be applied to the substrate by all conventional methods known to those skilled in the art, such as brushing, spraying, casting, dipping or electrophoretic coating.

Other substrates which can contain the compounds according to the invention are printing pigments and printing inks which can contain the customary pigments of inorganic or organic origin.

Although the compounds according to the invention exhibit excellent whitening effects on the substrates and application methods indicated above, most preferred is their application in the field of imaging and recording materials, especially in photographic recording materials. The invention therefore particularly preferably relates to image and recording materials, especially photographic recording materials, containing at least one compound of formula I. A particular recording material is photographic paper, which can be a paper especially for black-and-white or color printing.

In the case of photographic paper, the compound of formula I is incorporated into the base itself or into the paper coating (preferably a polyethylene layer).

However, it is equally possible to incorporate them into an enhanced silver halide layer and/or an unenhanced layer which is coated on the paper.

To further improve the white background of photo paper prints,
Advantageously, the fluorescent brightener, which is preferably a liquid, is dispersed in the gelatin layer and applied as one of the layers to the base. This has the following advantages.

(a) Only a small amount of fluorescent brightener has to be used since there is no loss during development.

(b) The introduced scattered light is free of unwanted light sources.

(c) A high amount of fluorescence is achieved.

The compound of 2) according to the present invention is liquid or related industry,
Very easily soluble or miscible with the typical high-boiling organic solvents used in particular in the photographic industry, the compounds do not tend to precipitate within the photographic layer.

If the compound of I is not already liquid, by mixing some compounds of formula I with low melting point or by mixing a liquid compound and a solid compound, it is liquid at room temperature and has the above advantages. A liquid product can be obtained.

If the brightener according to the invention is incorporated into the target material together with a solvent (dispersant), typical examples of such solvents are: phthalates (e.g. dimethyl, diethyl, diptyl, cyamyl, dihexyl, diheptyl, Dioctyl,
dinonyl or didecyl phthalate, or dibutyl chlorophthalate), glycolates (e.g. butyl butylphthalyl glycolate), phenols (e.g. 2,4-
di-n-amylphenol, 2゜4-di-tertiary amylphenol), phosphates (e.g. diphenyl, triphenyl, tricresyl, talesyldiphenyl, dioctyl, dioctylbutyl, trioctyl, tridecyl,
trixylenyl, tri(isopropylphenyl), tributyl, trihexyl, trinonyl, trioleyl or tri(butoxyethyl) phosphate, citrates (e.g. triethyl, tributyl, trihexyl, trioctyl, trinonyl or tridecyl-0-acetyl citrate), benzoates (e.g. butyl , hexyl, heptyl, octyl, nonyl, decyl, undecyl, tetradecyl, octadecyl or oleyl benzoate), esters of substituted benzoic acids (e.g. butyl 2-methoxybenzoate, pentyl 0-methylbenzoate, decyl p-methylbenzoate, lauryl O −
chlorobenzoate, propyl 2,4-dichlorobenzoate, oleyl 2,4-dichloropenzoate or octyl p-methoxybenzoate), fatty acid esters and dicarboxylic acid esters (e.g. hexadecyl myristate, dibutyl sebacate, dibutoxyethyl succinate) esters of polyols (e.g. decamethylene glycol diacetate, triacetyl- or tributylglycerol, pentaerythritol tetracapronate, or isosorbitol cycaprylate), fatty acid amides (e.g. N,N-dimethyl-1N,N-diethyl- or N,N-dibutyl laurylamide), chlorinated paraffins, aliphatic or aliphatic-aromatic ethers (e.g. glycerol, trialkyl ethers, glycerol 1,3- dialkyl ether, n-pentadecyl phenyl ether or 3-pentadecyl phenylethyl ether), alkylaryl carbamate (e.g. ethyl N, N-diphenyl carbamate) or mixtures of said liquids, and furthermore at least one chlorine atom, especially JP- A 61-124,
939.

The compounds according to the invention may be used in the above process in conjunction with other fluorescent brighteners, such as other thiophene derivatives, such as in particular US Pat. National Patent No. 61-124,9
39, as well as other groups of fluorescent brighteners, such as oxazoles, stilhenes, coumarins, thiazoles, imidazoles, imidasilones, pyrazoles or naphthalimides, such as those described above, e.g. JP 61-124 , 939.

The compounds according to the invention can be incorporated, for example, in various layers of photographic paper, for example as described in European Patent Application No. 1
Ultraviolet absorbers are also commonly incorporated, as described in US Pat. In this case, the brightener and UV absorber can be incorporated in the same layer or in different layers. If it is desired to incorporate the thiophene derivatives according to the invention into the gelatin layer of recording materials, in particular photographic papers, surface-active compounds usually have to be added. Advantageously, these nonionic or anionic surfactants are used, such as alkali metal salts of alkyl sulfates, alkylaryl sulfates, alkylaryl ether sulfates or alkylaryl polyether sulfates, alkyl succinates, etc. It can be.

In order to obtain as fine a dispersion of the compound according to the invention in the desired medium as possible, the compound is homogenized with the medium, preferably in equipment of the type of homogenizer, colloid mill, high speed stirrer or ultrasonic mixer. Additionally, thiophene brighteners can be dissolved in low boiling point (e.g. less than 150°C) solvents, miscible with water and then removed prior to application to the base (e.g. For example, it is removed by blowing.

Examples of such low-boiling solvents are listed below: alkyl acetates (e.g. methyl, ethyl, n-propyl, isopropyl or butyl acetate, methyl or ethyl propionate), ethyl formate, diethyl carbonate, lower chloroalkanes ( (e.g. carbon tetrachloride, dichloroethylene, trichloroethylene, 112-dichloropropane, chloroform or amyl chloride), ketones (e.g. acetone, methyl ethyl ketone, diethyl ketone or methyl isobutyl ketone), ethers (e.g. diisopropyl ether, dibutyl ether, tetrahydrofuran or dioxane), alcohols (e.g. methanol, ethanol, isopropanol or butanol), monoethers of diols (e.g. ethylene glycol monomethyl or monoethyl ether), hydrocarbons (e.g. cyclohexane, methylcyclohexane, ligroin, benzene, toluene or xylene), nitromethane, acetonitrile, dimethyl Sulfoxide, N
- methylpyrrolidone, dimethylformamide, tetrahydrothiophene dioxide, butyrolacetone or 1°2-dimethoxyethane.

The thiophene compounds according to the invention can also be used in photographic systems with hydrophobic latex spaces. Therein, the thiophene compound can be present both in solution and in latex particles. Examples of such Larinxes and their general use with fluorescent brighteners are found, for example, in U.S. Pat.
It is described in No. 337.

As already mentioned, the fluorescent brighteners according to the invention can be incorporated into the desired image-generating layer or recording material. They can be present alone in separate layers or in layers containing further active compounds, such as UV absorbers, color couplers, oxidized developing substances and/or scavengers for silver halides. However, since subsequent fluorescent brighteners manifest themselves more effectively,
Preferably they are located in one or more layers disposed above the layer containing the UV absorber described above.

Photographic materials containing thiophene derivatives according to the invention are
There is no need to develop in a special bath.

However, the benefits may be further improved by adding water-soluble fluorescent compounds to the development bath, especially since such compounds reduce haze caused by dye sensitization. Examples of such water-soluble fluorescent compounds that can be used with the thiophene derivatives according to the present invention include U.S. Pat.
195, in particular the following formula: (wherein A represents a morpholino group, dimethylamino group, diethylamino group or methoxy group, and B represents the following formula; % formula %) N(CH2CHzOH) z or a group represented by the following formula:).

The fluorescent brighteners according to the invention can also be used in X-ray films, for example those for medical use. They are very suitable for incorporation into such base polyesters, for example together with one or more blue dyes, creating a more transparent blue shadow in the film. However, they can be incorporated into one or more layers of the film, and this can be done using the methods already described.

The method also allows incorporation into other types of photographic films, such as transparent materials, if blue fluorescence is desired.

The thiophene derivatives according to the invention can also be incorporated into other desired photographic materials, such as photocomposing paper, by methods analogous to those described above, and the photographic images are
It can be obtained by a silver dye bleach method, a silver dye diffusion transfer method, a silver salt diffusion method, or a heat development or "dry silver" method.

When brightening imaging and recording materials, the use of the thiophene brighteners according to the invention is not limited to materials sensitized by halides (eg paper). They are photopolymerized,
Photoplasticization, based on the destruction of microcapsules containing heat- or light-sensitive diazonium salts, white dyes and oxidizing agents, thermal dye diffusion, thermal color-forming diffusion, dye lactones and Lewis acids, or dyes or colorless color-forming agents It can also be used in printing systems and color forming systems. Furthermore, the compounds of formula ■ can be used in electrostatic printers, electrophotographic printers, electrophoretic printers, magnetographic printers, or laser electrophotographic printers or inkjet printers, thermal bubble inkjet printers, thermal transfer printers or dot matrix printers or pen plotters. can be included in a liquid recording material.

Furthermore, the present invention also relates to imaging and recording materials containing at least one compound of formula I.

The amount of fluorescent brightener of formula I added to a particular material can vary within wide limits, depending on the field of application. In the imaging and recording materials mentioned above, they can be added, for example, in amounts of 1 to 500 mg, in particular in amounts of 2 to 250 mg, preferably in amounts of 550 mg per square meter of said material.

Compounds of formula I can be prepared in a manner known per se. Examples of such methods are shown in US Pat. No. 3,136,773 and US Pat. No. 4,267,343.

For example, 1 molar equivalent of thiophenedicarboxylic acid or a functional derivative thereof represented by the following formula (2): is combined with a total of about 2 molar equivalents of an 0-aminophenol represented by the following formula (2) and/or Va: as appropriate. If the reaction is carried out in the presence of a catalyst at an elevated temperature, the resulting reaction intermediate of formula The process continues directly to the final product of formula I.

As functional derivatives of dicarboxylic acids (2), in particular their lower esters and especially their halides, especially their chlorides are used.

If the process is carried out in one step, the reaction temperature is e.g.
20-260"C1, especially 160-260°C, and the reaction is advantageously carried out under an atmosphere of an inert gas, such as nitrogen gas. Preferably, a catalyst, especially an acidic catalyst, such as boronic acid, chloride Zinc, polyphosphoric acids including p-toluenesulfonic acid or birophosphoric acid are added.

The amount of catalyst is, for example, from 0.5 to the weight of the reaction mixture.
It is 5%. The reaction may be carried out in the melt using a solvent. Examples of such solvents are dimethylformamide and etherizable hydroxy compounds, such as evapopropylene glycol, ethylene glycol monoethyl ether or diethylene glycol diethyl ether.

If the process is carried out in two stages, the first stage advantageously comprises the presence of an organic solvent, for example an aromatic hydrocarbon optionally substituted with halogen or nitro, such as evabenzene, toluene, xylene, chlorobenzene, dichlorobenzene or nitrobenzene. It can be carried out below. Here, the reaction temperature is, for example, 40 to 150°C, especially 50°C.
~120°C. Advantageously, the reaction mixture is heated to the reflux temperature of the solvent used. Second stage (ring closure reaction)
is preferably carried out under the preferred reaction conditions described in the first step.

Details of the described manufacturing method are provided in U.S. Patent No. 3.136.
．． No. 773 and the Examples below.

Some of the compounds 2) can also be produced by converting the compounds obtained by the above method into other compounds of the formulas shown.

Therefore, starting from a compound in which X in substituents R1 to R4 represents -C00H, a compound in which X represents -COOR' (R9 represents H) can be obtained by ordinary esterification or salt formation. , also amine (HNRI!R”
) can give compounds in which X represents -CONR"R" (advantageously carried out after previous conversion to the acid chloride). On the contrary, the free acid (X = −C00
H) is the obtained ester (X=-COOR'(R' represents H, cation)) or amide (X--CONR
1! R'') can be obtained from rucotoni by saponifying it.

Further, other esters can be obtained by transesterification of the above-mentioned esters, and other amides can be obtained by transamidation of the above-mentioned amides. A suitable method is
It is well known to those skilled in the art.

The starting compounds of the formula Va are known or can be prepared by methods known per se. They couple, for example, a phenol of the following formula (■) or the following formula (■a) with a diazonium salt (for example, a diazonium salt from aniline), respectively:
The resulting azo compound is reductively cleaved to produce the corresponding 0-aminophenol. Otherwise, the phenol of formula ■ or ■a can be nitrated by conventional nitration methods, followed by the resulting compound of formula ■ or ■a
: By reducing the 0-nitrophenol represented by the following by a conventional method, for example, by catalytic reduction, it is possible to obtain the corresponding 0-aminophenol of the formula (1) or Va.

Phenols of formula (1) or (2)a are known or can be produced by known methods.

In this regard, reference is made, for example, to EP-A 106.799. 0-Nitrophenol of formula (1) or (2)a and the process for its preparation are also described, for example, in EP-A 323.408.

Thiophenedicarboxylic acids and their functional derivatives (2) are known and can be produced by known methods. See, e.g., US-^3,136,773.

Another possibility for the preparation of the compounds according to the invention is the reaction of a sulfide of the formula (IX) with a dicarbonyl compound of the formula X or a derivative thereof.

The compound of 2) has the following formula XI: X-Co-CH2-3-CH2-Co-X (X
I) of formula V and/or Va in 2 molar equivalents. b) by reacting a compound of the formula X and/or XIIa of the formula xn and/or XIIa with sodium sulfide; [Ia: Obtained by reacting a compound represented by (XI[Ia) with a compound of the above formula X■ or XIIa.

The above compounds of X■ and X■ or XI[a or It can be prepared by reacting the hydrochloride of a 2-mercaptoacetimide alkyl ether with an aminophenol of formula V or Va.

Details of the above method can be obtained from US Pat. No. 4,267.343.

Finally, compound No. 2 can also be prepared according to the reaction formula below.

red here is a reducing agent, For example, copper is shown.

The following examples illustrate the invention in further detail. Throughout the examples, the rest of the detailed description, and the claims, parts and percentages are by weight unless otherwise indicated.

Example 111: 1891 g of methyl 3-(3-tert-butyl-4-hydroxyphenyl)-propionate are dissolved in 2700 d of toluene and 1 g of sodium nitrate is added to the solution. 1008g of 67% nitrous acid aqueous solution and 1 part of water
000- mixture, then slowly increase the reaction temperature to 5-1
Add while maintaining at 0°C.

The reaction mixture is then stirred for a further 18 hours at room temperature.

The organic layer is then separated, washed with NaHCO3 solution and water, and concentrated. The residue is distilled under high vacuum and the product distills out at 153-160°C/10-'mm/Hg. This produces methyl 3-(3-tert-butyl-4-hydroxy-
1509 g of 5-nitrophenyl)-propione-) are obtained.

The following formula shown in Table 1 below: Nitrophenol is expressed as in a similar way It can be manufactured more easily.

Table 1 Example 13: Methyl 3-(3-tert-butyl-4-
Hydroxy-5-nitrophenyl)-propionate (
For example, 1597 g (obtained according to Example 1) are dissolved in 16 f of ethyl acetate. This solution is hydrogenated for 23 hours using a Raney nickel catalyst under a hydrogen pressure of 5 bar. Thereafter, the catalyst is filtered off under N2 atmosphere and the filtrate is concentrated. As a residue, 7L of methi with a melting point of 108-109°C
1299 g of /3-(3-tert-butyl-4-hydroxy-5-aminophenyl)-propionate are obtained.

The following formula shown in Table 2 using a similar method: A compound represented by is obtained.

Table 2 Table 2 a) The product is used directly in the next step without isolation.

Example 25: Thiophene-2,5-dicarboxylic acid was dispersed in 400 d of toluene and dimethylformamide 4
Add ml. Thionyl chloride is added dropwise at 70"C. The resulting mixture is refluxed under nitrogen atmosphere for 5 hours. Excess thionyl chloride is then distilled off and methyl 3-(3tert-butyl-4-hydroxy-5- 132.5 g of aminophenyl)-propionate are added.

Generation of HCI and yellow precipitate are observed. The reaction mixture is stirred for a further 4 hours at 80° C. under a nitrogen atmosphere and then allowed to cool. The precipitate is filtered off, washed with toluene and dried under reduced pressure. This produces a yellow powder with a melting point of 172-173 °C of the formula: 2.2-bis-[3-tert-butyl-2
-Hydroxy-5-(2-methoxycarbonyl-1-ethyl)-phenylaminocarbonylcorchioffene 21
2g is obtained.

The following formula shown in Table 3 using a similar method: A compound represented by is obtained.

Implementation ■ Dish: 2.5-bis-[3-tert-butyl 2-hydroxy-5-(2-methoxycarbonyl-1-ethyl)-
89.3 g of phenylaminocarbonyl coachophene was ground with 1 g of boric acid and heated at 230°C under an argon atmosphere.
Heat to. The resulting reaction water is distilled off. At this temperature 6
After some time, no more water evaporates. The light brown residue is treated in ethanol to precipitate the product. After filtration and drying, 2,5-bis-[7-tert-butyl-5-(2
2 g of -methoxycarbonyl-1-ethyl)-benzoxazol-2-ylcorchioffene are obtained.

The following formula shown in Table 4 using a similar method: A compound represented by is obtained.

Kayagamiomote backyard ±487 2. 5-bis-[7-tert-butyl-5
-(2-methoxycarbonyl-1-ethyl)-benzoxazol-2-ylcorchioffene (see Example 36)
10 g, n-octan-1ol and 0.3 g of dibutyltin oxide were heated at 120 °C with stirring,
The mixture is further stirred at this temperature for 5 hours. The methanol produced is distilled off. Filter the reaction mixture (@Prolith R
apid) and then washed with CHIC1.

The filtrate is concentrated and excess 1-octatool is distilled off under reduced pressure. The residue is recrystallized from methanol. As a result, 2,5-bis-[7-tert-butyl-5-(n-octoxycarbonyl-1-ethyl)-benzoxa Sol-2
- 7.7 g of il-coch-offene are obtained.

The following formula shown in Table 5 using a similar method: A compound represented by is obtained.

Table 5 Example 75: KOH22 in methanol 120h+1
Dissolve 4.4g. 229 g of 2,5-bis-(7-tert-butyl-5-(n-methoxycarbonyl-1-ethyl)-benzoxazol-2-ylcorchioffene) are added and the mixture is stirred under reflux for 2 hours. After cooling, the bis-sodium salt of the acid obtained precipitates out.Filter and evaporate the mother liquor.The combined solids are dispersed in 32.
Acidify with ml of concentrated hydrochloric acid. The solid is filtered off and washed with water 52 until neutral. The crude product thus obtained was recrystallized from boiling ethanol at 2°C and heated to 100°C under reduced pressure.
Dry at C. This yields 2,5-bis-(7-tert-butyl-5-(2
-carboxy-1-ethyl)-benzoxazole-2-
200 g of ilcochiofene are obtained.

m measurement: 14.80 g of 2.5-bis-(7-tert-butyl-5-(2-carboxy-1-ethyl)-benzoxazol-2-ylcorchioffene) was mixed with thionyl chloride 3
0.0g, and heat to 80°C while stirring well until hydrochloric acid generation stops.

Excess thionyl chloride was removed under reduced pressure, leaving a residue of 2,5-bis-[7-tert-butyl-5-(2-chlorocarbonyl-1-ethyl)-benzoxazol-2-yl]-thiophene. Dry the toluene 50” in 300 d
Dissolve in C. At this temperature, 12.0 g of bis-(2-ethylhexyl)-amine and 5.0 g of triethylamine
are simultaneously added dropwise over 15 minutes, cooled, washed with dilute hydrochloric acid and water, dried and the solvent is distilled off under reduced pressure. Apply the residue to a silica gel column. This produces a viscous oil, pure 2,5-bis-(7-tert-butyl-5
-(2-OJ, N-di-2-ethylhexyl-amide)
19.5 g of -1-ethyl]-benzoxazol-2-yl)-thiophene are obtained.

Example 77: By the method described in Example 76, using 2-ethylhexylamine instead of bis-(2-ethylhexyl)-amine, the melting point was 175-176°C.
2,5-bis-(7-tert-butyl-5-(2
-(N-2-ethylhexylamido)1-ethyl]-benzoxazol-2-yl)thiophene is obtained.

Using a mixture of alcohols in the transesterification process according to Example 48 typically yields a liquid mixture of compounds of formula I.

In Example 48, if a 1:1 mixture of n-octan-1-ol and 2-ethylhexan-1-ol was used instead of n-octan-1-ol, the following formula: The following three components (1) Ra=n Ca Hlt, Rb=n
c9 Hlt(2) Ra=n Co Hlt, R
b = 2 m-tylhexyl (3) Ra = 2-1-tylhexyl, Rb = 2
An isomer mixture of compounds having -1 tylhexyl in amounts in a ratio of approximately t:2:i is obtained.

The mixture is an oily liquid.

1 ship ■ Neck: In Example 48, 2-ethylhexane-1-ol and 2-ethylhexane-1-ol were used instead of n-octan-1-ol.
Using a 1:1 mixture of -methylpentan-1-ol, the formula described in Example 78 has the following three components: (1) Ra = 2-ethylhexyl, Rb = 2-ethylhexyl (2) An isomer mixture of the compound is obtained having Ra=2-ethylhexyl, Rb=2-methylpentyl (3) Ra=2-methylpentyl, Rb=2-methylpentyl in amounts in a ratio of about 1:2:1.

The mixture is an oily liquid.

When using a 1:1 mixture of diethylene glycol monoethyl ether and diethylene glycol mono-n-butyl ether in place of n-octan-1-ol in Example 48, the formula described in Example 78 It is represented by the following formula: and the following three components (3) R = -CH2CH20CJC)120-n-CbHgR
,,w -CH2CH20C)licl(20-n-C
An isomer mixture of compounds having an amount of J* in a ratio of approximately t:2:X is obtained.

The mixture is an oily liquid.

Back panel ■: In Example 48, if a 1:1 mixture of two alcohols represented by the following formula: An isomer mixture of a compound having the following formula:

The mixture is an oily liquid.

1 cliff ■ Low: Preparation of gelatin layer containing thiophene derivative according to the invention Gelatin 1250 mg Tricresyl phosphate 510 mg 4.8-diisobutylnaphthalene 100 mg -2-sulfonate (
Surfactant) Curing agent (2-hydroxy-4+6 80 mg dichloro-1,3,5-)riazine) Ethyl acetate 700 mg Compound of formula I to be tested 0.4 mmol To this is added deionized water to make up to 24 ml.

The resulting coating composition was applied to a transparent polyester film using a plate-coating implementation for 24 hours.
Coat to a thickness of μm and dry. A protective layer of gelatin is then formed by dipping the film in gelatin.

b) Measurement of Fluorescence The fluorescence of the film samples obtained above is measured in a @ Shimadzu UV-240 UV-visible spectrophotometer equipped with an impregnated sphere (tllbricht's 5phere). After automatic calibration with barium sulfate as a reflector in both channels, a UV filter (Kodak @Wra
tten 2C) between the sphere and the photocell, then base line collection between 900 and 420n.
Perform between n+. Set absorption at 470 nm to 0. Next, measure the energy mode (gear width 5n)
m) is carried out between 420 nm and 300 nm. 380
The first maximum value below nm is used for evaluation.

This measuring device measures the total fluorescence as a function of the excitation frequency, which is obtained in a simple manner.

Below 380 nm, all of the excitation light is absorbed by the UV filter, so the values measured in this range are accurate.

Since the excitation light is only incompletely filtered in that region, 3
Accurate measurements are not possible between 80 nm and 420 nm.

All values are measured relative to standard samples. The results are summarized in Table 6 below.

Table 6 *) Standard Uraju Masuzu: A gelatin layer containing some of the other compounds of formula I was prepared according to the method described in Example 82. The amount of fluorescence of the fluorescent brightener in the gelatin layer on the polyester base was determined by the Eitle-Ganz method (textilvered
elung 3.389-392 (1968))
Measured by The results obtained are shown in Table 7.

Table 7 Example 84: Production of polyethylene film Polyethylene granules (LDPE, ■Coethylene HL257
8) is dry mixed in each case with 0.25% (based on the weight of polyethylene) of the compound according to Example 36 or Example 37. The mixture is then converted into a 30 μm thick film at 140° C. in a Schwabentane extruder.

Fluorescence is measured as described in Example 82. It has been found that polyethylene films exhibit high levels of fluorescence.

Example 85: a) Polyester granules 100 of the type @Terlenka matt (containing 0.5% TiO2)
0g, GeO type in drying cabinet, 110°
C. for 16 hours, followed by 2 hours at 160.degree. C., then cooled to 70.degree. C. and filled into preheated standard wear joint bottles. Then 5 g of the compound of formula I to be tested
is added to each case and after tightly closing the bottle, it is completely cooled and mixed in a Cyril mixer until the compound of formula I is evenly distributed over the granules (check under UV lamp). Compound 2 is finely powdered before being added to the granules.

The polyester granules thus treated are spun into filaments. The bottle is opened just before spinning. Carry out in a Fourne spinning unit under the following conditions: Spinning temperature: 275”C/280°C/258°C
°C; Drawoff: 500m/min; Spinning metal: 34 holes 10.25m1II; Stroke L/Tching: 100'C
Te 1:4; vA density 130734 Tenier: Spinning finish: @Limazol ZE+ 15% (in water).

b) The filament obtained according to a) at 40
Roll it up into 12 piles with a width of 40 m on 170 mm thick paper.

C165At to the filament at a black bulb temperature of 63±3°C.
ASTM in 1as Weatherometer
Irradiation is carried out according to 626-77. After the period shown in Table 8 has ended, samples are taken and checked for yellowness (Yl, a measurement of color change) using a MacBeth colormeter according to ASTM D 72-1920. The results are shown in Table 8.

Table 8 Yellowness (after ~ hours) Compounds of Examples
0 7 25 125 205 345c)
Filament obtained according to a) 40 x 170
Roll it up into 12 piles with a width of 40 mm on 1/2 inch thick paper.

The whiteness of the filament is measured in a Zeiss RFC-3 spectrophotometer. The white value is CTB
Δ-GEIGY white scale (CIB^-GEIGY-
Rundschau 1973/1. pages 10-12)
Calculated by The values obtained are shown in Table 9 below.

d) The filaments obtained according to a) are made into a knitted stocking consisting of three filaments. Roll these up into 4 piles on 40X170 IIIm cardboard. The light fastness of the fluorescent brightener of formula I contained in the filament was determined according to Standard Test Method 15O105/BO2, 1984 (
Exposure to xenon lamp, compare with blue scale).

Table 10 shows the results. indicates the value of

Table 10

Claims (1)

[Claims] (1) The following formula I: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) [In the formula, R_1 and R_3 each independently represent an alkyl group having 1 to 8 carbon atoms, a cyclopentyl group, cyclohexyl group, C7-C9 aralkyl group, phenyl group or the following formula: -C_mH_2_m_+_1_-_q(X)_q(II)
(In the formula, m represents a number from 0 to 10, and q is 1 or 2.
and when m represents 0, q represents 1), and R^2 and R^4 each independently represent a group represented by the above formula II, or R When ^1 and R^3 each represent the meaning expressed by the above formula II, R^2 and R^4
can each independently represent an alkyl group having 1 to 8 carbon atoms, a cyclopentyl group, a cyclohexyl group, an aralkyl group having 7 to 9 carbon atoms, or a phenyl group, and R^5 and R^6 each independently represent hydrogen atom, methyl group,
represents an ethyl group or together represents a trimethylene or tetramethylene group, and X is a) of the formula: -COOR^9, where R^9 is a hydrogen atom;
an alkali metal ion or equivalent alkaline earth metal ion, a C1-C30 alkyl group, a C1-C18 hydroxyalkyl group, a C3-C20 alkyl group, or at least one -O −
a hydroxyalkyl group of 3 to 20 carbon atoms, unsubstituted or substituted with OH and/or an alkyl group of 1 to 4 carbon atoms;
2 cycloalkyl group, C2 to C30 alkenyl group, C7 to C15 aralkyl group,
Glycidyl group, furfuryl group or the following formula: -CH_2-
CH(OH)-R^1^0 (wherein R^1^0 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aralkyl group having 7 to 9 carbon atoms, or the following formula: -CH_2O
R^1^1 (in the formula, R^1^1 is the number of carbon atoms 1 to 1
8) represents a group represented by an alkyl group, cyclohexyl group, phenyl group, tolyl group or benzyl group,
Or R^9 is the following formula: -(CH_2)_pP(O)(OR^1^6)(OR^
1^7) or -(CH_2)_pP(O)(OR^1
^6) -R^1^8 (in the formula, p represents 1 to 6, and R^1^6, R^1^7 and R^1^8 are the following d
b) The following formula: -CONR^1^2R^1^3 (wherein, R^1^2 and R^1^ 3 is each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkyl group having 3 to 20 carbon atoms with at least one -O- interposed therebetween, or an unsubstituted or alkyl group having 1 to 4 carbon atoms. and/or C5 -C12 cycloalkyl groups substituted with OH, phenyl groups or C1 -C12 alkyl groups, C1 -C4 alkoxy groups and/or substituted with halogen atoms Phenyl group: alkenyl group having 3 to 18 carbon atoms,
represents C7-C12 aralkyl or C2-C4 hydroxyalkyl, or R^1^2 and R^1^3 taken together represent C4-C5 alkylene; a group or -O- or the formula:
-N(R^1^5)-(In the formula, R^1^5 is a hydrogen atom,
represents an alkyl group having 1 to 18 carbon atoms, a cyclohexyl group, an alkenyl group having 2 to 6 carbon atoms, a phenyl group, an alkylphenyl group having 7 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms)
(represents an alkylene group having 4 to 6 carbon atoms interposed with a group represented by), c) a group represented by the following formula: -OR^1^
4 or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^1^4 is a hydrogen atom, the number of carbon atoms is 1 or 1
C5-C12 alkyl group, C5-C12 cycloalkyl group, C5-C12 cycloalkyl group substituted with OH and/or C1-C4 alkyl group, C3-C18 alkyl group represents an alkenyl group, a phenyl group or an aralkyl group having 7 to 20 carbon atoms, and R^2^0 represents an alkenyl group having 1 to 18 carbon atoms;
an alkyl group, a cyclohexyl group, an alkenyl group having 2 to 18 carbon atoms, a phenyl group, an alkylphenyl group having 7 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms), d) The following formula: -P(O) (OR^1^6) (OR^1^7
) or -P(O)(OR^1^6)-R^1^8 (wherein, R^1^6 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and R^1^7 has 1 carbon atom
represents an alkyl group having 1 to 12 carbon atoms, and R^1^8 represents an alkyl group having 1 to 12 carbon atoms or a phenyl group)
or e) a group represented by the following formula: ▲There are numerical formulas, chemical formulas, tables, etc.▼ (wherein R^1^9 represents an alkyl group having 1 to 12 carbon atoms) A compound represented by (2) The compound according to claim 1, wherein in the above formula I, R^1 and R^3, and R^2 and R^4 are each the same. (3) The compound according to claim 1 or 2, wherein R^1 and/or R^3 in the above formula I represent an alkyl group having 1 to 4 carbon atoms, a cyclohexyl group, or a group represented by the above formula II. . (4) In the above formula I, R^1 and/or R
4. The compound according to claim 3, wherein ^3 represents an alkyl group having 1 to 4 carbon atoms, particularly a tert-butyl group, a cyclohexyl group, or a group represented by the following formula: ▲ Numerical formula, chemical formula, table, etc. ▼. (5) In the above formula I, R^1 and R^3 are the same,
5. A compound according to claim 4, which is a C1 -C4 alkyl group, in particular a tert-butyl group. (6) In the above formula I, R^1 and R^3 have 1 carbon atom
to 4 alkyl group, cyclohexyl group, benzyl group, or a group represented by the above formula II, R^2 and R^4
is a group represented by the above formula II, or when R^1 is a group represented by the above formula II, an alkyl group having 1 to 8 carbon atoms, a cyclopentyl group, a cyclohexyl group, or a phenyl group having 1 to 8 carbon atoms. 3, m represents 0 to 6, R^5 and R^6 each independently represent a hydrogen atom, a methyl group or an ethyl group, and R^7
is hydrogen atom, C1-C18 alkyl group, cyclopentyl group, cyclohexyl group, C2-C18 alkenyl group, phenyl-C1-C3 alkyl group, furfuryl group, 1-4 C alkyl group, -O-
an alkyl group having 3 to 18 carbon atoms, or having the formula: -(CH_2)_pP(O)(O having 1 to 6 carbon atoms)
(alkyl) (in the formula, p represents 1 to 6), R^1^2 and R^1^3 each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms; , cyclopentyl group, cyclohexyl group, phenyl group, alkyl group having 1 to 4 carbon atoms, phenyl group substituted with methoxy group and/or chlorine atom, 3 to 1 carbon atoms
8 alkenyl group, benzyl group or C2-C4 hydroxyalkyl group, or R^1^
2 and R^1^3 together have 4 to 5 carbon atoms
alkylene group or -O-, -NH- or -N(
CH_3)- represents an alkylene group having 4 to 5 carbon atoms, R^1^4 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cyclohexyl group, or a cyclohexyl group having 3 carbon atoms.
represents an alkenyl group having 1 to 6 carbon atoms, a phenyl group or a benzyl group, and R^1^5 is an alkyl group having 1 to 8 carbon atoms, a cyclohexyl group, an alkenyl group having 2 to 6 carbon atoms, a phenyl group, a tolyl group or a benzyl group; represents a group, R^1^6 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R^1^7 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
2. A compound according to claim 1, wherein R^1^8 represents an alkyl group having 1 to 8 carbon atoms, and R^1^9 represents an alkyl group having 1 to 8 carbon atoms. (7) The compound according to any one of claims 1 to 6, wherein in the above formula I, X represents a group represented by the following formula: -COOR^9 or -CONR^1^2R^1^3. (8) In the above formula I, R^2 and/or R^4 are in the above formula II, q represents 1 or 2, and m is 0 to 6
or when R^1 and/or R^3 represent a group represented by the above formula II, R^2 and/or R^4 are an alkyl group having 1 to 8 carbon atoms, 8. A compound according to claim 1, which is cyclopentyl, cyclohexyl or phenyl-C1-C3alkyl. (9) In the above formula I, R^1 and R^3 are the same,
represents an alkyl group having 1 to 4 carbon atoms or a group represented by the above formula II, R^2 and R^4 are the same and represent a group represented by the above formula II, or R^1 and When R^3 represents a group represented by the above formula II, R^2 and R^4 can also represent an alkyl group having 1 to 4 carbon atoms,
m represents 0 to 6, and X represents the following formula: -COOR^9 or -CONR^1^2R^1^3(
In the formula, R^9 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 3 to 18 carbon atoms, a furfuryl group, a cyclohexyl group, a phenyl-alkyl group having 1 to 3 carbon atoms, 1 to C 3 -C 18 alkyl group with 4 -O- groups present, or of the formula: -(CH_2)_p'P(O)(OC 1 -C 4 alkyl group, in which p' is 1 to 4), and R^1^2 and R^1^3 each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. (10) In the above formula I, R^1 and R^3 represent an alkyl group having 1 to 4 carbon atoms or a group represented by the above formula II, and R^2 and R^4 represent a group represented by the above formula II. or when R^1 and R^3 represent a group represented by the above formula II, R^2 and R^4 can also represent an alkyl group having 1 to 4 carbon atoms. , m represents 0 to 6,
And The compound according to claim 9, which represents an alkyl group having 3 to 12 carbon atoms. (11) At least one type of fluorescent brightener as claimed in claim 1.
Organic materials containing compounds of formula I as described. 12. The material of claim 11, which is a synthetic polymer, such as a thermoplastic. (13) A material according to claim 12, which is a coating material, preferably a lacquer or a dispersible paint. (14) The material according to claim 11, which is a coloring composition for printing or a printing ink. (15) The material according to claim 11, which is an image-forming or recording material, in particular a photographic recording material. (16) The material according to claim 15, which is photographic paper. (17) A material according to claims 11 to 13, containing the compound of formula I in an amount of 0.0001 to 2% by weight. (18) For inkjet printing, dye diffusion transfer printing, thermal wax transfer printing and dot matrix printing, or for use in electrostatic printers, electrographic printers, electrophoretic printers, magnetographic printers and laser electrophotographic printers. 16. A material according to claim 15, which is an image-receiving layer or a recording material. (19) Microcapsules based on the principle of photopolymerization, photoplasticization, heat- or light-sensitive diazonium salts, white dyes (leucodyes), and oxidizing agents, dye lactones plus Lewis acids, or containing dyes or colorless color formers. 16. A material according to claim 15, which is a pressure-sensitive paper or recording material based on the principle of destruction. (20) The material according to claim 15, which is a pressure intensifying film or a radiation storage film for medical radiology and can be excited by light. (21) from 1 to 500 mg, and in particular from 2 to 250 mg, of the compound of formula I per square meter of the specified material;
Claims 15, 16, or 18 to 2 containing in an amount of
0. The material according to any one of item 0. (22) A method for fluorescent whitening of organic materials, characterized in that at least one compound of the formula I according to claim 1 is mixed into or applied to the organic materials.